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Advanced Problems
in

Organic Chemistry
for

IIT-JEE
By : M.S. Chouhan
1. Several factors (steric, electronic, orbital interactions etc.) can affect the inversion barrier of an amine. In the given pair which data is correctly placed ? i Pr Me

(a)

Me

Me

vs

i Pr +

Me

(b)

G = 0.2 D kcal/mol D kcal/mol G = 7.9 Me Cl | | vs N N Me Me (c) (d*) All of these Cl Cl

+ +

N Me Me G = 7.0 D kcal/mol D kcal/mol G = 20.5

vs

2.

+ D kcal/mol D kcal/mol G = 7.9 G = 22.9 Circle represent most acidic hydrogens in these molecules. Which of the following is correct representation ? O OH MeO2C

(a)

OH CF3

(b)

HO

CO2H

S (c) 3. (d*) All of these F The pH at which maximum hydrate is present in an solution of oxaloacetic acid, is : | | | | | | H -- 2 -O -- C C C CH O H pK a = 2.2 (a*) pH = 0 pK a = 3.98 (b) pH = 12 (c) pH = 4 (d) pH = 6

O O

2 4. Which of the following isomeric hydrocarbons is most acidic ? (a) (b*) (c)

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(d)

5.

Compound A and B, both were treated with NaOH, producing a single compound C. O O CH3 + OH
(A)

CH3 C. Compound (C) is :

heat HO-

OH
(B)

O O (a*)
14

C CH3 (b) O (c)

O (d)

C label OTs no label

6.

; Product of above reaction is : OCOR (b) (d) None of these

RCO2 H

OCOR (a) (c*) both a and b CH3O OCH3

CN

7.

+ B) 2 ( A) (
CH3O (C) CCH3

150 C

H C = CN = CH

Compound (B) reacts acrylonitrile to give (C), structure of compound (A) is : CH2 OCH3 (a) (b*) (c) CH2 (d)

Get Ready for IIT-JEE 8. Increasing order of rate of reaction with HNO3 H2 SO4 is :
O O (i) O O O O O O O (ii) O O O

(iii)

(a) iii < ii< i (c) i < iii < ii

(b) ii < iii < i (d*) i < ii < iii

9.

Match the columns I, II and III (Matrix). Column-I Reaction Column-II Nature of product formed Column- IIII Number of chiral center present in product. (Consider only one isomer in case of racemic mixture or Diastereomer)

(a) CH3

2 CCl 4 (p)

Br

Racemic mixture

(w)

(b) CH3

2 CCl 4 (q)

Br

Meso

(x)

(c) CH3
CH 3

Br2 (r) CCl 4

Diastereomer

(y)

H C= =C CH3

(d)
H

Br2 CCl4

(s)

Vicinal dihalide

(z)

4
H3C H OH H

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10.
H HO Ethynylestradiol (1) H

The synthetic steroid ethynylestradiol (1) is a compound used in the birth control pill. A. B. C. D. E. How many sp 3 hybridised carbon atoms are present in compound (1)? (a) 8
2

(b) 9 (b) 5

(c) 10 (c) 6

(d) 11 (e) 12 (d) 7 (e) 8 (e) 10

How many sp hybridised carbon atoms are present in compound (1) ? (a) 4 How many sp hybridised carbon atoms are present in compound (1) ? (a) 2 (b) 4 (c) 6 (d) 8

Which of the following functional group is contained in compound (1) ? (a) A ketone (b) An alcohol (c) A carboxylic acid (d) An ester How many asymmetric (stereogenic) centres are present in compound (1) ? (a) 2 (b) 3 (c) 4 (d) 5

1.

In the preparation of iron from haematite (Fe 2O 3 ) by the reaction with carbon Fe 2O 3 + C 2 Fe + CO How much 80% pure iron could be produced from 120 kg of 90% pure Fe 2O 3 ? (a*) 94.5 kg (b) 60.48 kg (c) 116.66 kg (d) 120 kg

2.

1 van der Waals constant b of helium is 24 mL mol - molecular diameter of helium. . Find 10 8 (a) 1.335 cm (b) 1.335 cm 10 10 8 (c*) 2.67 cm 10 8 (d) 4.34 cm 10 -

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There exist an equilibrium between solid SrSO 4 and Sr 2+SO 2- aqueous medium. and 4 ion in The possible equilibrium states are shown in figure as thick line. Now, if equilibrium is disturbed by addition of (a) Sr(NO 3 ) 2 and (b) K 2SO 4 and dotted line represent approach of system towards equilibrium. Match the columns given below :

(iii)

Sr2+

(iv)
2 SO4

Sr2+

(v)
2 SO4

Sr2+

(vi)
2 SO4

Sr2+

2 SO4

(I) addition of Sr(NO3 ) 2 (II) addition of K 2SO 4 (a) (I) (iii), (II) (iv) (b*) (I)(iv),(II) (v) (c) (I) (vi), (II) (v) (d) (I) (iv), (II) (v) 4. Determine the potential of the following cell : Pt|H 2 ( g , 0.1 bar )|H +10 3 M )||MnO ( aq, 0.1 M ), ( aq, 4 2+ + Mn ( aq, 0.01 M ), H ( aq, 0.01 M )|Pt Given : E
MnO4| Mn 2+

= 1.51 V (b*) 1.48 V (c) 1.84 V (d) none of these

(a) 1.54 V 5.

0.1 M KI and 0.2 M AgNO 3 are mixed in 3 : 1 volume ratio. The depression of freezing point 1 of the resulting solution will be [ K f ( H 2O) = kg mol 1.86 K ]: (a) 3.72 K (b) 1.86 K (c) 0.93 K (d*) 0.279 K (d) 0.268 In an atomic bcc, what fraction of edge is not covered by atoms? (a) 0.32 (b) 0.16 (c*) 0.134

6. 7.

Select the correct statement(s) : (a*) A solution is prepared by addition of excess of AgNO 3 solution in KI solution. The charge likely to develop on colloidal particle is positive. (b*) The effects of pressure on physical adsorption is high if temperature is low (c) Ultracentrifugation process is used for preparation of lyophobic colloids. (d) Gold number is the index for extent of gold plating done For a first order homogeneous gaseous reaction, A 2B + C If the total pressure after time t was Pt and after long time (t then k in terms of ) was P and t Pt , P is : P 2P 2.303 2.303 (a) k = log (b) k = log t P Pt t P Pt 2 2.303 P (c*) k = log t 3(P Pt ) (d) none of these

8.

9.

Fixed mass of an ideal gas contained in a 24.63 L sealed rigid vessel at 1 atm is heated from -to 27 73 C C. Calculate change in Gibbs energy if entropy of gas is a function of temperature as S = 0.1 kJ) 2 + T (J/K): (Use 1 atm L = 10 2 (a) 1231.5 J (b) 1281.5 J (c*) 781.5 J (d) 0

6 10.
Column-I

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Column-II

(A) Orbital angular momentum of an electron (B) Angular momentum of an electron in an orbit (C) Spin angular momentum of an electron (D) Magnetic moment of atom

(P) (Q)

h s( s + 1) 2p n( n + 2)

(R) nh 2p (S) h l( l + 1) 2p

* Answer : A S, B R, C P D Q , 11. Which is the correct order of ionization energies? (a) F > F > Cl > Cl (b*) F > Cl > Cl > F (c) F > Cl > Cl > F 12. (d) F > Cl > F > Cl Ionization energy of an element is : (a*) Equal in magnitude but opposite in sign to the electron gain enthalpy of the cation of the element (b) Same as electron affinity of the element (c*) Energy required to remove one valence electron from an isolated gaseous atom in its ground state (d) Equal in magnitude but opposite in sign to the electron gain enthalpy of the anion of the element O 2 F2 is an unstable yellow orange solid and H 2O 2 is a colourless liquid, both have OO bond and OO bond length in H 2O 2 and O 2 F2 respectively is : (a) 1.22, 1.48 (c) 1.22, 1.22 14. (b*) 1.48 , 1.22 (d) 1.48, 1.48

13.

Which of the following equilibria would have highest and lowest value of K p at a common temperature. (a*) BeCO 3 (b) CaCO 3 BeO + CO 2 CaO + CO 2 (c) SrCO 3 (d*) BaCO 3 SrO + CO 2 BaO + CO 2 In the structure of H 2CSF4 , which of the following statement is/are correct? (a*) Two CH bonds are in the same plane of axial SF bonds (b) Two CH bonds are in the same plane of equatorial SF bonds (c*) Total six atoms are in the same plane (d) Equatorial SF plane is perpendicular to plane of p -bond

15.

16.

In the isoelectronic series of metal carbonyl, the CO bond strength is expected to increase in the order : (a) [Mn(CO) 6 ]+ (b*) < 6 ] < 6 ][Cr(CO) [V(CO) [V(CO)6 ]< 6 ] <[Mn(CO)6 ]+ [Cr(CO) (c) [V(CO) 6 ]<[Mn(CO) 6 ]+ < 6] [Cr(CO) (d) [Cr(CO) 6 ] <[Mn(CO) 6 ]+ < 6 ][V(CO)

Get Ready for IIT-JEE 17. [Fe(H 2O) 6 ]2+ and [Fe(CN) 6 ]4 differ in : (a) geometry, magnetic moment (c*) magnetic moment, colour 18. (b) geometry, hybridization (d) hybridization, number of d-electrons

Which of the following statements is true ? (a) In [PtCl 2 (NH 3 ) 2 ]2+ the cis form is optically inactive while trans form is optically active (b*) In [Fe(C 2O 4 )3 ] 3 , geometrical isomerism does not exist while optical isomerism exists (c) In Mabcd, square planar complexes show both optical as well as geometrical isomerism (d) In Mabcd tetrahedral complex, optical isomerism cannot be observed

19.

The CFSE for [(CoCl) 6 ]4 complex is 18000 cm 1 . The D 4 ]2 will be : for [CoCl (a) 18000 cm 1 (b) 16000 cm 1 B
Yellow solution Y

(c*) 8000 cm 1 C
Deep blue solution

(d) 2000 cm 1

20.

A
Pale yellow solution

A
Regenerated

The sequential unknown reagents is/are: (a) H 2O 2 /neutral medium, H 2O 2 /H+ , Cu 2+ salt solution (b*) H 2O 2 / H+ , H 2O 2 / OH -3+ salt solution , Fe (c) H 2O 2 /OH -O 2 /H + salt solution , H2 , Co 2+ (d) H 2O 2 /neutral medium, H 2O 2 /OH - salt solution , Fe 2+ 21. Selectcorrectstatement(s): (I) When excess FeCl 3 solution is added to K 4[Fe(CN) 6 ] solution, in addition to is also Fe III [Fe II (CN) 6 ]- [Fe III (CN) 6 ]- formed due to side redox reaction , Fe II (II) When FeCl 2 is added to K 3[Fe(CN) 6 ] solution, in addition to Fe II [Fe III (CN) 6 ], III II Fe [Fe (CN) 6 ] is also formed due to side redox reaction (III) Fe III [Fe II (CN) 6 ]is paramagnetic while Fe II [Fe III (CN) 6 ]is diamagnetic (IV) Fe III [Fe II (CN) 6 ]is diamagnetic while Fe II [Fe III (CN) 6 ]is paramagnetic (a*) I, II 22. (b) III, IV (c) both (a) and (b) (d) None of these

Column-I (Pair of com plexes)

Column-II (Property which is similar in given pair)

(A) [Fe(CN) 6 ]3 and [Co(NH 3 ) 6 ]2+ (B) [Fe(H 2O) 6 ]2+ and [Fe(CN) 6 ]4 (C) [Ni(CN) 4 ]4 and [Ni(CO) 4 ] (D) [Ni(H 2O) 6 ]2+ and [NiCl 4 ]2

(P) Magnetic moment (Q) Geometry (R) Hybridisation (S) Number of d-electrons

* Answer : A P Q, R; B Q, S; C P Q, R, S; D P S , , ,

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PASSAGE

PASSAGE
H 2O CO2

1
SO2 Na 2S/ I 2 Ag + / salt

Na B plex) A C D E (com
D

a.

The compound B and C are : (a) Na 2CO 3 , Na 2SO 4 (c*) Na 2CO 3 , Na 2SO 3 The compound D is : (a) Na 2SO 4 (b) Na 2S 4O 6

(b) NaHCO 3 , Na 2SO 4 (d) None of these (c) Na 2S 2O 5 (d*) Na 2S 2O 3 (d) +5, 1

b. c.

Oxidation number of each S atom in compound D : (a) +2, +2 (b) +4, 0 (c*) +6, 2

PASSAGE

PASSAGE
a. b. c.

The molecule in which an atom is associated with more than 8 electrons is known as hypervalent molecule and less than 8 electrons is known as hypovalent molecule. All hypervalent molecules must have dp -pp but the molecules having back bonding bonding need not to have always dp -pp -bonding. Which of the molecule is not hypovalent but completes its octet : (a) AlCl 3 (b) AlBr2 (c*) AlF3 Which of the following molecule is having complete octet : (a) BeCl 2 (dimer) (b) BeH 2 (dimer) (c) BeH 2 (s) Which of the following molecule is not having dp -pp : -bonding (a) SO 2 (b) P4O10 (c) PF3 (d) BF3 (d*) BeCl 2 (s) (d*) B 3 N 3 H 6

PASSAGE

PASSAGE

An unknown mixture contains one or two of the following : CaCO 3 , BaCl 2 , AgNO 3 , Na 2SO 4 , ZnSO 4 and NaOH. The mixture is completely soluble in water and solution gives pink colour with phenolphthalein. When dilute hydrochloric acid is gradually added to the solution, a precipitate is formed which dissolves with further addition of the acid. a. Which of the following combination of compounds is soluble in water? (a) BaCl 2 and AgNO 3 (b) AgNO 3 and NaOH (c) BaCl 2 and Na 2SO 4 (d*) ZnSO 4 and excess NaOH The aqueous solution of mixture gives white precipitate with dil. HCl which dissolves in excess of dil. HCl. It confirms: (a) BaCl 2 + (b) Na 2SO 4 + NaOH NaOH (c*) ZnSO 4 + (d) AgNO 3 + NaOH NaOH The white precipitate is: (a) ZnSO 4 (c*) Zn(OH)2 (b) Na 2ZnO 2 (d) ZnCl 2

b.

c.

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Mechanics
for

IIT-JEE Vol. 1
By : Er. Anurag Mishra
Initially blocks A and B are given impulse in opposite directions as shown in figure. Now we have to calculate the : (i) Maximum stretch in spring B A 2 0 0 (ii) Maximum velocity of block A and B in ground m 2m frame. (iii) Minimum velocity of block A and B in ground (a) frame. Fig. 4.21 ( 2m)( 2 m 0 0)Sol. = CM = 0 3m 1. At initial instant
v A CM =-g = v A g v CM 0i v B CM =-g =i v B g v CM 2 0

At maximum stretch Initial state 0 0 2 B/CM = A/CM = 0 m 2m 0 0 l0+ xm CM frame CM frame (b) Fig. 4.21

From work energy equation in CM frame We get w spring = D CM KE system 1 2 1 ( 2m)( m) 2 - = kX m 0 ( 3 0) 2 2 ( 2m + m) 1 2 1 2 ( 3 kX m = ) 2 m 0 2 2 3 or 6m Xm = 0 k

10
Blocks return to relaxed state

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Block diagrams representing situation when block returns to relaxed state

m m (c) Fig. 4.21

2 B/CM = 0

A/CM = 0 2m 0

What appears in CM frame

0 A/g = 3

B/g = 0 2m

What appears in ground frame

When spring again regains its natural length in CM frame.

Most Important Concept

v A ground = v A CM + ground v CM frame frame frame

similarly

v B ground = v B CM + ground v CM frame frame frame

Note that velocity of any block in ground frame is superposition of two velocity vectors, velocity of block in CM frame and velocity of CM with respect to ground.
v A ground is maximum when v A CM has maximum magnitude and is in same direction as vector frame frame v CM ground . frame

Similarly v A ground is minimum when v A CM

frame

frame

and v CM ground vectors are in opposite direction.

frame
|vB/CM| = 0 B CM frame Fig. 4.22 0 |vA/CM| = 2 A 0

| v A max | = | v A CM |+ ground | = | v CM 2 0 frame frame

Similarly

v B max | = | v B CM | + ground | = | v CM 3 0 frame frame

Minimum velocity of A is attained when block is at equilibrium

position (spring is relaxed) and v A CM and v CM g are

opposite to each other. Thus | v Amin | = 0

Minimum velocity of B is attained at the instant B is moving toward left (opposite v CM ) and velocity magnitude is figure) 0 (see Thus | v Bmin | = 0

Get Ready for IIT-JEE 2. Two blocks A and B of masses 2m & 3m placed on smooth horizontal surface are connected with a light spring. The two blocks are given velocities as shown when spring is at natural length.
2m A Fig. 4E.30 K 3m B

11

Column-I (A) minimum magnitude of velocity of A ( during motion Amin ) (P)

Column-II 5 0 7 5

(B) maximum magnitude of velocity of A ( during motion (Q) Amax ) (C) maximum magnitude of velocity of B ( Bmax )during motion (R)

(D) velocity of centre of mass ( the system comprised of (S) CM ) of blocks A, B and spring

Sol.

Step I: ( 3m )- 3m = CM = 5m 5 Step 2: In COM frame Initial velocity of Initial velocity of 6 A= to - = left 5 5 4 4 B == to right - = 5 5 5

Blocks are executing SHM in CM frame with initial position as equilibrium position Step III: Velocity variation of B in ground frame, considering right as +ve form so 4 3 to 4 + + = = 5 5 5 5 5 & | 0 | min |= Bmax | = B 6 7 6 to - = + = + 5 5 5 5 5 when spring is at maximum extension. 5

Velocity variation A in ground frame from

Thus minimum velocity of A is

12 3. The 10 kg block is resting on the horizontal surface when the force 'F' is applied to it for 7 second. The variation of 'F' with time is shown. Calculate the maximum velocity reached by the block and the total time 't' during which the block is in motion. The coefficient of static and kinetic friction are both 0.50. Block begins to move when F= m N =100 = 0.5 50N from t =t = 0 to 4 sec F= 2st 0 t 4 = 40N 4< t 7 Block begins to move at t = after that 2 sec. md Fm N= dt d 25t 50 = 10 dt
4

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F(N) 100

10 kg

F 40

Sol.

4 (a) Fig. 2E.60

t(s)

N N mg (b) Fig. 2E.60 F

or,

d .5 5)dt (2 =t
0 2

2 . 5t 2 = 5t 2
2

= 5m s After t = 4 sec.; block retards due to greater friction force Velocity of block at t = 7 sec (i.e. 3 sec. after force becomes 40 N) 1 = 3 5= 2m s At t = force F is now only friction acts 7 sec. - a s = 10 a =2 5m s 0 =) 2(s t t = 4 sec. Total time interval for which block moves t = to t = 2 sec. 7.9 sec i.e., 5.4 sec.

5m/s initial = F = 40N kN = 5 0 N (c) Fig. 2E.60

Get Ready for IIT-JEE 4. A force of 20 N is applied to a block at rest as shown in figure. After the block has moved a distance of 8m to the right the direction of horizontal component of the force F is reversed in direction. Find the velocity with which block arrives at its starting point. Stage 1: Motion till force reverses its direction N = F sin 37 mg 3 = 20 20 5 = 8N F cos 37N = - ma m k 4 20 25 - 8= 0. 2 a 5 a =2 7m s Velocity of block after displacement of 8 m = s = 12 m 2 7 8

13

37 =0.25 m=2kg (a) Fig. 2E.61 Fsin37 N Fcos37 kN mg=20N (b) Fig. 2E.61

Sol.

Concept
Kinetic friction is opposite to relative velocity it opposes relative motion. When horizontal component force is reversed, relative velocity is not changed therefore, direction of kinetic friction does not change.
Fsin37 Fcos37

Stage 2:
k N

m s = 112

is reversed, block continues along original direction, but due to retardetion created F cos 37 by m F cos 37 travels till it stops. block N and k -37 N ) ma ( F cos += m k 4 - +7 ( 20 . 25 (0 8) = 2 a 5 or, a = s2 9m
2 0 =2as; 2 s= 2 a (112) 56 == m 2 9 9

Displacement of block in this phase

14 Stage 3: Which block returns its a acceleration is: F cos 37N = - mg m k a =2 7m s Velocity of block when it returns to original position
2 as = 2

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Fsin37 Fcos37 N

mg (c) Fig. 2E.61

k N

56 = + 2 7 8 9 16 7 m s = 3 5. A carriage of mass M and length l is joined to the end of a slope as shown in the figure. A block of mass m is released from the slope from height h. It slides till end of the carriage (The friction between the body and the slope and also friction between carriage and horizontal floor is negligible) Coefficient of friction between block and carriage is mminimum h in the given terms. . Find M l m l (a) m (b) 2 m 1+ 1+ m M m m l l (c) m (d) m 2+ 1+ M M
m h

smooth

Fig. 2E.102

Sol.

Concept:
Block slips relative to carriage, use relative motion equations of kinematics.

velocity of block, just before reaching carriage 2gh 0 = Now acceleration of block

N A a1

N A mg mg a2

mg mg m mg a1 = -= m g mg m (b) m mg acceleration of carriage a2 = Fig. 2E.102 M considering this moment as t = 0, motion of block as seen from carriage

u rel = 2gh 0 = m arel = 2 = + a1 -- a m g 1 M Relative velocity of block when block moves through distance x with respect to carriage 2 2 arel x rel = 2 rel + m when x = = m l, 0 2gh = + 2 g l 1 rel M m h= m l 1+ M

Covering all the possible types of problems like numerical problems, objective problems, MCQ, matching type questions, integer answers type questions, previous years questions, comprehension based objective type problems & assertion reason type problems etc.

Algebra
for

IIT-JEE
By : M. Uma Shankar & Dr. J.V. Rao
A Complete text book for IIT-JEE aspirants. Covering all the possible types of problems like numerical problems, objective problems, MCQ, matching type questions, integer type questions, previous years questions, comprehension based objective type problems, etc.

Conceptual Inorganic Chemistry

By : Prabhat Kumar

Conceptual Physical Chemistry

By : Prabhat Kumar & Adarsh Kumar

Objective Physics

Objective Physics
(IIT-JEE & AIEEE) (IIT-JEE & AIEEE)

is

Entrance Exam.

goal